Method of manufacturing a superconducting pattern by light irradiation

ABSTRACT

A superconducting ceramic film is deposited on a substrate sputtering. In virtue of the low thermal conductivity of ceramic, a laser beam is radiated to the ceramic film in order to remove the irradiated portion by sublimation and produce a pattern on the ceramic film.

This a divisional of application Ser. No. 07/174,503, filed Mar. 28, 1998, now U.S. Pat. No. 4,957,900.

BACKGROUND OF THE INVENTION

This invention relates to a method of manufacturing a superconducting pattern by light irradiation.

There have been known the use of metallic materials such as Nb₃ Ge, with which it is possible to wind a coil to form a superconducting magnet having a high Tc since a metallic material has a high ductility and malleability. On the otherhand, such a metallic material requires the use of liquid helium when operated in superconduction. In recent years, superconducting ceramics are attracting interest of reserchers which have a high Tc.

However, such superconducting ceramics are fragile because of low ductility and malleability so that it is entirely impossible to form a superconducting coil with a wire made of such superconducting ceramics.

SUMMARY OF THE INVENTION

It is therefore an object of the invention to provide a high Tc superconductor in the form of wire or strip.

It is therefore an object of the invention to provide a method of manufacturing a high Tc superconductor in the form of wire or strip which is suitable for mass-production.

In accordance with one aspect of the present invention, an oxide (or carbonate) mixture for constituting a superconducting ceramic is first formed in the form of a thin film on a substrate by sputtering, printing such as screen press printing or other methods. When deposited by sputtering, the structure of the ceramic material of the film becomes amorphous or another structure which are abundant in lattice defect or imferfection so that the resistivity of the ceramic material is usually rather high. The deposited ceramic can be transformed into a desired superconducting ceramic by thermal oxidation or firing.

The inventor has found that such a ceramic type superconducting film can be easily processed by laser scribing accompanied by sublimation since its thermal conductivity is relatively small. The ceramic film can be processed by laser irradiation before or after firing. For example, a strap of the ceramic material can be removed or remains on a substrate. In this invention, any laser can be employed which is suitable for the case, such as a YAG laser (1.06 micron in wavelength), an excimer laser (KrF, KrCl and so forth), a CO₂ laser or an N₂ laser. A YAG laser can emit a laser beam having a circular cross section repeatedly at 5 to 100 KHz. When an excimer laser is used, a shaped beam having a cross section of a circle (10-100 microns in diameter) or a linear cross section (10-40 cm wide 5-100 microns long) can be obtained by (expanding and) squeezing with an optical system.

BRIEF DESCRIPTION OF THE INVENTION

FIG. 1 is a perspective view showing a manufacturing process of superconducting ceramic pattern in accordance with the present invention.

FIG. 2 is a perspective view showing another embodiment of the manufacturing process of superconducting ceramics in accordance with the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring to FIG. 1, a manufacturing process in accordance with the present invention will be described In FIG. 1(A), a substrate 1 is made of a caramic material such as alumina, silicon oxide, silicon nitride, alminium nitride, strontium titanate, zirconia, yttria or YSZ(yttria stabilized zircon), or a metal such as copper or a copper alloy or glass. YSZ, yttria or zirconia are particularly suitable for this case from the view point of the coefficient of thermal expansion rate. Anyway the material should be selected so that the differential coefficient of thermal expansion between the underlying substrate and the ceramic thin film to cover them should be limited preferably within 50% of the ceramic thin film. If the coefficients of the substrate and the ceramic thin film are substantially different, strain may hinder the ceramic film from being recrystallized into superconducting structure by thermal annealing. On the substrate 1 is formed a ceramic film 2 conforming to YBa₂ C₃ O₆₋₈ with 0.1 to 50 micron in thickness, e.g. 20 microns by spattering or printing method such as screen press printing.

The ceramic film 2 is fired at 500-1000° C., e.g. 900° C. for 15 hours and transformed to a superconducting structure. A laser beam having a wavelength of 1.06 microns from a YAG laser is radiated to the superconducting film 2 to produce a pattern thereon. The surface of the film is scanned to the right direction from the left edge as shown in FIG. 1 so that a portion of the film is removed by sublimation leaving a groove 3. The appropriate output power is 10⁶ to 10⁷ W/sec. Stronger irradiation may damage the underlying substrate 1. Alternatively, the laser patterning can be effected before the firing step which transforms the ceramic film into a superconducting structure in which oxygen and copper atoms form a layer-structure.

An excimer laser instead of the YAG laser may be used which is capable of emitting a series of intense laser pulses with a rectangular cross section of 20×30 mm² for example. The pulse is shaped into a linear cross section 10 cm wide and 50 microns thick. Each circular pulse is radiated to an irradiating region prescribed on the film which shares a 60-80% area with the irradiating region for the preceding pulse (and also of the subsequent pulse). The scanning speed is 2 m/min. The frequency is 5-30 KHz, e.g. 10 KHz. By virtue of this irradiation, the irradiated portions of the ceramic film are selectively removed by sublimation. The entire substrate may be heated during the laser processing to 300-800° C., e.g. 600° C. by a halogen lamp.

FIG. 2 shows second embodiment of the invention. In this embodiment, substantially same procedure is repeated as the preceding embodiment except described below.

The substrate 1 is a cylinder. On the substrate is deposited a ceramic film 2 while the substrate 1 is rotating in the direction indicated by an arrow 12. After drying the film, a laser beam having a 50 microns diameter is radiated repeatedly to the substrate. The position of the laser beam is shifted to the right direction (the axial direction of the cylinder 1) while the substrate 1 is rotating around its axis. By this process, a continuous helical supercondutor 5 is formed on the cylinder 1. Each part of the helix 5-1 is isolated from the adjacent part 5-2 by the helical groove 3 which has been removed by laser sublimation. As a result, a superconducting electromagnet in the form of a coil is constructed.

When laser annealing is utilized in addition to laser sublimation, an advanced process can be performed. First, a ceramic film is formed on a surface in such a way that the film does not have yet superconducting structure. A presciribed portion of the film is melted by irradiation with a laser beam (laser annealing). The irradiated portion is endowed with superconducting property by recrystallization during cooling. In the same time, the ceramic film may be cooled if necessary. Then, another prescribed portion of the ceramiq film is removed by laser sublimation. By this process, ceramic pattern which may be composed of superconducting regions and non-superconducting (insulating) regions can be obtained. Whether a laser irradiation is effected as sublimation or annealing is depending on the laser emission condition (laser power or intensity).

Superconducting ceramics for use in accordance with the present invention also may be prepared in consistence with the stoichiometric formulae (A_(1-x) B_(x))_(y) Cu_(z) O_(w), where A is one or more elements of Group IIIa of the Priodic Table, e.g., the rare earth elements, B is one or more elements of Group IIa of the Periodic Table, e.g., the alkaline earth metals including beryllium and magnesium, and x=0-1; y=2.0-4.0, preferably 2.5-3.5; z=1.0-4.0, preferably 1.5-3.5; and w=4.0-10.0, preferably 6.0-8.0. One example is YBa₂ Cu₃ O₆₋₈. Also, superconducting ceramics for use in accordance with the present invention may be prepared consistent with the stoichiometric formulae (A_(1-x) B_(x))_(y) Cu_(z) O_(w), where A is one or more elements of Group Vb of the Priodic Table such as Bi, Sb and As, B is one or more elements of Group IIa of the Periodic Table, e.g., the alkaline earth metals including beryllium and magnesium, and x=0.3-1, y=2.0-4.0, preferably 2.5-3.5; z=1.0-4.0, preferably 1.5-3.5; and w=4.0-10.0, preferably 6.0-8.0. Examples of this general formula are BiSrCaCuCu₂ O_(x) and Bi₄ Sr₃ Ca₃ Cu₄ O_(x). Tc onset and Tco samples confirmed consistent with the formula Bi₄ Sr_(y) Ca₃ Cu₄ O_(x) (y is around 1.5) were measured to be 40-60° K, which is not so high. Relatively high critical temperatuers were obtained with samples conforming to the stoichiometric formulae Bi₄ Sr₄ Ca₂ Cu₄ O_(x) and Bi₂ Sr₃ Ca₂ Cu₂ O_(x). The number designating the oxygen proportion is 6-10, e.g. around 8.1.

While a description has been made for several embodiments, the present invention should be limited only by the appended claims and should not be limited by the particular examples. 

What is claimed is:
 1. A superconducting coil comprising a support and at least one spiral turn of a superconductor, which is composed of a compound oxide represented by the formula:

    (A.sub.1-x B.sub.x).sub.y Cu.sub.z O.sub.w

where A is one or more element of Group IIIa of the Periodic Table, B is one or more elements of Group IIa of the Periodic Table, and x=0-1.0; y=2.0-4.0; z=1.0-4.0 and w=4.0-10.0, wherein said support is made of an insulator, and comprises a material selected from the group consisting of alumina, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon.
 2. A superconducting coil produced by placing a superconducting material on a surface of a support, and then heating the superconducting material to a temperature at which the superconducting material is sintered to a superconductor wherein said superconductor is composed of a compound oxide represented by the formula:

    (A.sub.1-x B.sub.x).sub.y Cu.sub.z O.sub.w

where A is one or more elements of Group IIIa of the Periodic Table, B is one or more elements of Group IIa of the Periodic Table, and x=0-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0, wherein said support comprises a material selected from the group consisting of alumina, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon, copper and copper alloy.
 3. A superconducting coil as in claim 2 wherein said superconducting material is a compound oxide represented by the general formula:

    Y.sub.1 Ba.sub.2 Cu.sub.3 O.sub.6-8.


4. A superconducting coil as in claim 2 wherein said support has an exterior surface and where said superconductor is disposed on said exterior surface of the support.
 5. A superconducting device comprising:a substrate having a superconducting ceramic layer on a surface of said substrate, said superconducting ceramic comprising (A_(1-x) B_(x))_(y) Cu_(z) O_(w) where A is one or more elements of Group IIIa of the Periodic Table, B is one or more of the alkaline earth metals, and x=0-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0 and said substrate is made of a material which has a thermal expansion coefficient of 50-150% of that of said superconducting ceramic layer, said superconducting ceramic layer having a portion thereof removed to form a predetermined pattern in said superconducting ceramic layer, wherein said support comprises a material selected from the group consisting of alumina, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon, copper and copper alloy.
 6. The device of claim 5 wherein said substrate surface is a periphery of a cylinder and said predetermined pattern is a helix provided on said periphery to form a superconducting coil.
 7. A superconducting device as in claim 5 wherein said substrate has an exterior surface and where said superconducting ceramic layer is disposed on said exterior surface of the substrate.
 8. A superconducting device comprising:a substrate having a superconducting ceramic layer on a surface of said substrate, said superconducting ceramic comprising (A_(1-x) B_(x))_(y) Cu_(z) O_(w) where A is one or more elements of Group Vb of the Periodic Table, B is one or more of the alkaline earth metals, and x=0.3-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0 and said substrate is made of a material which has a thermal expansion coefficient of 50-150% of that of said superconducting ceramic layer, said superconducting ceramic layer having a portion thereof removed to form a predetermined pattern in said superconducting ceramic layer, wherein said support comprises a material selected from the group consisting of alumina, silicon oxide, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon, copper and copper alloy.
 9. The device of claim 8 wherein said substrate surface is a periphery of a cylinder and said predetermined pattern is a helix provided on said periphery to form a superconducting coil.
 10. A superconducting device as in claim 8 wherein said substrate has an exterior surface and where said superconducting ceramic layer is disposed on said exterior surface of the substrate.
 11. A superconducting device comprising:a substrate having a superconducting ceramic layer on a surface of said substrate, said superconducting ceramic comprising (A_(1-x) B_(x))_(y) Cu_(z) O_(w) where A is one or more elements of Group IIIa of the Periodic Table, B is one or more alkaline earth metals, and x=0-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0 and said substrate is made of a material selected from the group consisting of alumina, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, YSZ, copper, copper alloy, and glass, said superconducting ceramic layer having a portion thereof removed to form a predetermined pattern in said superconducting ceramic layer.
 12. The device of claim 11 wherein said substrate surface is a periphery of a cylinder and said predetermined pattern is a helix provided on said periphery to form a superconducting coil.
 13. A superconducting device as in claim 11 wherein said substrate has an exterior surface and where said superconducting ceramic layer is disposed on said exterior surface of the substrate.
 14. A superconducting device comprising:a substrate having a superconducting ceramic layer on a surface of said substrate, said superconducting ceramic comprising (A_(1-x) B_(x))_(y) Cu_(z) O_(w) where A is one or more elements of Group Vb of the Periodic Table, B is one or more alkaline earth metals, and x=0.3-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0 and said substrate is made of a material selected from the group consisting of alumina, silicon oxide, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, YSZ, copper, copper alloy, and glass, said superconducting ceramic layer having a portion thereof removed to form a predetermined pattern in said superconducting ceramic layer.
 15. The device of claim 14 wherein said substrate surface is a periphery of a cylinder and said predetermined pattern is a helix provided on said periphery to form a superconducting coil.
 16. A superconducting device as in claim 14 wherein said substrate has an exterior surface and where said superconducting ceramic layer is disposed on said exterior surface of the substrate.
 17. A superconducting coil produced by placing a superconducting material on a surface of a support, and then heating the superconducting material to a temperature range of 500-1000° C. to produce said superconducting coil wherein said superconductor is composed of a compound oxide represented by the formula:

    (A.sub.1-x B.sub.x).sub.y Cu.sub.z O.sub.w

where A is one or more elements of Group IIIa of the Periodic Table, B is one or more elements of Group IIa of the Periodic Table, and x=0-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0, wherein said support comprises a material selected from the group consisting of alumina, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon, copper and copper alloy.
 18. A superconducting coil as in claim 17 wherein said superconducting material is a compound oxide represented by the general formula:

    Y.sub.1 Ba.sub.2 Cu.sub.3 O.sub.6-8.


19. 19. A superconducting coil as in claim 17 wherein said support has an exterior surface and where said superconductor is disposed on said exterior surface of the support.
 20. A superconducting coil comprising a support and at least one spiral turn of a superconductor, which is composed of a compound oxide represented by the formula:

    (A.sub.1-x B.sub.x).sub.y Cu.sub.z O.sub.w

where A is one or more elements of Group Vb of the Periodic Table, B is one or more elements of Group IIa of the Periodic Table, and x=0.3-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0, wherein said support comprises a material selected from the group comprising alumina, silicon oxide, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon.
 21. A superconducting coil as in claim 20 wherein said support is a hollow cylindrical body.
 22. A superconducting coil as in claim 20 wherein said support has an exterior surface and where said at least one spiral turn of said superconductor is disposed on said exterior surface of the support.
 23. A superconducting coil produced by placing a superconducting material on a surface of a support, and then heating the superconducting material to a temperature at which the superconducting material is sintered to a superconductor wherein said superconductor is composed of a compound oxide represented by the formula:

    (A.sub.1-x B.sub.x).sub.y Cu.sub.z O.sub.w

where A is one or more elements of Group Vb of the Periodic Table, B is one or more elements of Group IIa of the Periodic Table, and x=0.3-1; y=2.0-4.0; z=1.0-4.0; and w=4.0-10.0, wherein said support comprises a material selected from the group consisting of alumina, silicon oxide, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon, copper and copper alloy.
 24. A superconducting coil as in claim 23 wherein said support has an exterior surface and where said superconductor is disposed on said exterior surface of the support.
 25. A superconducting material formed on a support comprising a material selected from the group consisting of alumina, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon, copper and copper alloy, wherein said superconducting material is composed of a compound oxide represented by the formula:

    (A.sub.1-x B.sub.x).sub.y Cu.sub.z O.sub.w

wherein A is one or more element of Group IIIa of the Periodic Table, B is one or more elements of Group IIa of the Periodic Table, and x=0-1.0; y=2.0-4.0; z=1.0-4.0 and w=4.0-10.0.
 26. A superconducting material formed on a support comprising a material selected from the group consisting of alumina, silicon oxide, silicon nitride, aluminum nitride, strontium titanate, zirconia, yttria, and yttria stabilized zircon, copper and copper alloy, wherein said superconducting material is composed of a compound oxide represented by the formula:

    (A.sub.1-x B.sub.x).sub.y Cu.sub.z O.sub.w

wherein A is one or more element of Group Vb of the Periodic Table, B is one or more elements of Group IIa of the Periodic Table, and x=0.3-1.0; y=2.0-4.0; z=1.0-4.0 and w=4.0-10.0. 